EP2689051B1 - Formulation aqueuse anticorrosion à base de silane - Google Patents

Formulation aqueuse anticorrosion à base de silane Download PDF

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Publication number
EP2689051B1
EP2689051B1 EP12706821.1A EP12706821A EP2689051B1 EP 2689051 B1 EP2689051 B1 EP 2689051B1 EP 12706821 A EP12706821 A EP 12706821A EP 2689051 B1 EP2689051 B1 EP 2689051B1
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weight
binder
gew
water
optionally
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German (de)
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EP2689051A1 (fr
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Philipp Albert
Eckhard Just
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a novel anticorrosive formulation based on an aqueous silane system as a binder, a process for their preparation and their use for coatings, in particular for the protection of metals from corrosion.
  • Aqueous silane systems are finding increasing interest because they contain less or no organic solvents and are therefore more environmentally friendly. In addition, these systems can be used without explosion protection. Stable, aqueous silane systems can not be prepared simply by mixing silanes with water, since many silanes are insoluble in the aqueous phase and hydrolyze and condense on contact with water. Therefore silane systems with organic solvents and defined amounts of water are usually used in corrosion protection. In order to modify the properties of the silane systems or to improve the corrosion protection, they can be formulated with additives, pigments and fillers.
  • DE 103 35 178 also describes the preparation of water-soluble silane systems, e.g. Example, a mixture of 3-aminopropyltrialkoxysilane and bis (trialkoxysilylpropyl) amine.
  • the silane mixture is hydrolyzed with a defined amount of water. But even here, the silane mixture contains 25 to 99.99% alcohol and is therefore not VOC-free.
  • composition of an aqueous solution which consists of a water-soluble aminosilane and an alkyltrialkoxysilane.
  • the Preparation is carried out by adding a defined amount of water to the silane mixture and subsequent temperature control at 60 ° C.
  • the silane mixture thus prepared is dissolved in water in a certain ratio and serves to hydrophobicize surfaces.
  • WO 2000/39177 describes the use of bis-silylaminosilanes and / or bis-silylpolysulfanes in aqueous solutions.
  • the silanes are mixed with water, an alcohol and optionally acetic acid and hydrolyzed for at least 24 hours. Subsequently, the application is carried out on metals.
  • Bis-silylaminosilanes are used in combination with other silanes and a metal chelate in aqueous solutions.
  • the silanes are partially hydrolyzed by aging for at least 2 weeks in aqueous concentrates. Subsequently, a metal chelate is added and further diluted with water.
  • all aqueous formulations contain after before the alcohol from the hydrolysis. The aqueous systems are used for the pretreatment of metal surfaces.
  • WO 2004/076718 relates to a process for coating a metallic surface with an aqueous solution containing a partially hydrolyzed silane such as.
  • a partially hydrolyzed silane such as.
  • fluorine-containing silane improves the hydrophobicity and corrosion resistance of the coating system.
  • the hydrolysis alcohol is not removed from the systems.
  • US 5,206,285 describes the preparation and use of water-based addition products of an epoxy and an aminosilane.
  • the aqueous silane systems are not solvent-free. They are used for metal coating and are intended to improve corrosion resistance.
  • EP 1 760 128 is claimed an aqueous two-component adhesive composition and their use for bonding or sealing.
  • One component of the coupling agent may contain a bis-silylaminosilane.
  • DE 10 2004 037 045 relates to aqueous silane nanocomposites prepared from glycidyloxypropylalkoxysilanes and aqueous silica sols in the presence of a catalyst.
  • the aqueous systems are virtually solvent-free and are suitable for metal coatings. Disadvantages are the high crosslinking temperatures of 200 ° C.
  • US 6,468,336 describes the formulation and application of a corrosion protection coating for steel.
  • the water-based formulation contains waterglass as a binder and as pigments, zinc, iron phyllosilicates and other fillers.
  • the formulations described should achieve excellent corrosion protection in layer thicknesses of 15 to 25 ⁇ m.
  • EP 1 191 075 teaches a water-based two-component system for corrosion protection coatings on steel.
  • the first component contains water, an aminoalkyltrialkoxysilane, an acid, an epoxysilane and conductive pigments.
  • the second component consists of zinc powder.
  • the finished mixture should allow a processing time of 16 hours.
  • the alcohol from the hydrolysis of the silane was not removed and the aqueous system was applied to give a dry film thickness of 25 microns.
  • the coated sheets showed no corrosion after 7 months of outdoor weathering.
  • WO 2000/46311 describes the treatment of metal substrates with a formulation of a ureidosilane, a multisilylsilane and a solvent.
  • the silanes are first partially hydrolyzed and then formulated.
  • the hydrolysis alcohol is not removed and the formulation is used without pigments.
  • a solvent-free corrosion protection primer is claimed.
  • the primer is composed of a stabilized silica sol, a phyllosilicate, a calcined aluminum phyllosilicate and zinc dust.
  • the dry layer thickness of the coating is about 15 to 25 microns. Abrasion resistance and working time were determined.
  • WO 2003/022940 describes a corrosion protection system consisting of an aqueous silica sol, optionally an organic resin, zinc dust and other additives.
  • the systems are characterized by abrasion resistance and pencil hardness.
  • WO 2006/079516 relates to an aqueous binder or coating agent based on an aminoalkylsilane or a formylaminopropyltrialkoxysilane and also an epoxysilane.
  • the binder is based on an aminoalkylalkoxysilane and an epoxy-functional alkoxysilane and a well-defined method of preparation.
  • the coating composition disclosed there was based on the binder with the addition of pigments, u. a. conductive pigments, and formulated additives.
  • WO 99/14277 describes an aqueous primer composition consisting of a reactive resin (dispersion), an organofunctional silane (amino or epoxy silane, no bis-silyl silanes) and a curing reagent. Bonding of metal substrates treated with this primer show very good strengths in combination with an epoxy resin in a shear test.
  • WO 2008/133916 describes a method for the treatment of metal surfaces.
  • the method involves treatment with an aqueous formulation consisting of hydrolyzed / condensed silanes.
  • the silanes used may be aminosilanes containing hydroxyl groups.
  • the coating systems produced in this way are not solvent-free.
  • the treated metal substrates were painted and show less infiltration at the scribe compared to the standard treatment.
  • US 6,929,826 claims a method for surface treatment of metals.
  • the method involves treatment with a formulation containing an epoxysilane and a tetraalkoxysilane.
  • WO 2006/137663 describes a composition consisting of an aminosilane and an epoxysilane.
  • the formulation contains a magnesium and vanadium compound and an acid. The preparation takes place in a water / alcohol mixture.
  • the metal substrates treated with this formulation show good corrosion resistance and good adhesion to organic coatings. The systems are not solvent-free.
  • WO 2009/059798 discloses a formulation and coating of a metal.
  • the formulation consists of tetraethoxysilane, vinyltrimethoxysilane, phenyltriethoxysilane, and propyltrimethoxysilane.
  • other components such as alcohols, catalysts, silica sols and additives are claimed.
  • Coatings must be heated to harden.
  • the formulation is intended to protect metal substrates from corrosion.
  • EP 0 274 428 teaches a composition consisting of an alkyltrialkoxysilane, a vinyltrialkoxysilane and / or other silanes such as an epoxysilane, an organic solvent and an aluminum sol.
  • WO 2009/030538 teaches aqueous compositions based on bisalkoxyalkylsilylamines, which are substantially free of organic solvents and also do not release alcohol when crosslinked. Furthermore, such systems can be based on further organosilanes. such as 3-glycidyloxypropyltrialkoxysilanes and alkylalkoxysilanes. The systems may also contain fillers, such as silica, titanium dioxide and aluminum oxide, and also color pigments. In addition, the process for the preparation and the application - including as anti-corrosion coating - disclosed.
  • Silanes and aqueous silane systems can, with appropriate formulation, form a coating on many substrates. These coatings can form no active corrosion protection, but only a passive corrosion layer and act as a binder or crosslinker in coating compositions (coatings). Thus, binders can also be seen as crosslinkers. Active corrosion protection can be achieved by corrosion inhibitors. In order to be able to produce such formulations, in particular environmentally friendly aqueous formulations, the binder and the anticorrosion additives must be compatible in order to provide the most stable and effective formulation possible and to be able to process it on an industrial scale within a reasonable time frame.
  • the present invention has the object to provide a further aqueous and largely VOC-free corrosion protection composition based on so-called bis-aminosilane cocondensates as a binder, which is compatible with particulate additives and optionally other additives substantially and as such at least several hours to weeks until are storage stable to the application.
  • a further aqueous and largely VOC-free corrosion protection composition based on so-called bis-aminosilane cocondensates as a binder, which is compatible with particulate additives and optionally other additives substantially and as such at least several hours to weeks until are storage stable to the application.
  • it was a particular concern that such formulations can be cured at room temperature and achieve good adhesion and corrosion protection on metal substrates.
  • the aim is that corrosion protection coatings obtainable on this basis can be applied in different layer thicknesses and can be overpainted after curing, ie achieve good adhesion to coatings, in particular to organic (paint) coatings.
  • cocondensates of an epoxyalkyl-functional alkoxysilane cf. the following formula I, with at least one bis-aminoalkyl-functional alkoxysilane, cf. also the following formulas II and IIa, and optionally further organofunctional alkoxysilanes or silica sol systems can produce special aqueous binder for corrosion protection formulations having a defined pH and a defined dry residue, which are largely VOC-free, in air at low temperatures, d , H.
  • Metal oxides or metal salts, and optionally further additives are advantageously compatible, stable on storage and are suitable for application.
  • Binders are usually liquids which can adhere solids with a fine degree of dispersion, furthermore can have a crosslinking effect in a preparation and allow adhesion to the substrate.
  • the binder For a formulation to be made from a binder and a particulate additive, the binder must be compatible with the additive, ie, it must wet the additive. As a result, the additive can be distributed in the binder and the positive Properties of the system are obtained.
  • formulations of a binder and additive can find wide application in corrosion protection.
  • aqueous systems are particularly advantageous since they contain essentially no organic solvents or other environmentally hazardous substances.
  • Aqueous sol-gel systems are not only environmentally friendly, but also very variable and very versatile. New aqueous binders based on aqueous sol-gel systems can not only cure at low temperatures, but also improve the adhesion of further coatings to these systems, ie they are well overcoatable.
  • aqueous binders are very versatile. They can be used as the basis for various formulations, in particular as a binder in combination with particulate metals and / or particulate metal compounds and optionally other additives. If the system has hydrophobic properties, then in addition to the epoxy-functional alkoxysilane and the bis-amino-functional alkoxysilanes and an alkyltrialkoxysilane can be used as another component.
  • aqueous binder system special properties of the aqueous binder system or special functions for coupling to an organic coating system are required, it is also possible to use further organofunctional silanes or else tetraalkoxysilanes in addition to the epoxy-functional alkoxysilanes and the bis-amino-functional alkoxysilanes.
  • the ratios of the silane components can be advantageously adjusted so that the fully hydrolyzed and condensed product in the aqueous solution is stable and still cures at low temperature on the substrate or as a binder in the formulation. But not only the ratio, but also the order of the dosage has a significant influence on the product properties.
  • the hydrolysis alcohol is advantageously removed from the reaction system during the preparation of the binder so that a largely VOC-free aqueous product can be provided.
  • the active ingredient of the binder usually consists of completely hydrolyzed and at least partially condensed or co-condensed silanes.
  • the solids content of the pure epoxy-functional alkoxysilane in the aqueous sol-gel system may advantageously be up to 70% by weight, while the solids content of the pure bisaminofunctional alkoxysilane should only be at most about 10% by weight. without getting stuck.
  • the dry residue (also referred to herein as solids contents) of the condensates or cocondensates in the binder is preferably in the range from 1 to 50% by weight, more preferably between 3 and 45% by weight and most preferably between 5 and 35% by weight. %.
  • composition of the invention may advantageously be present as a one-component system and used.
  • a composition of the invention has a dry residue (solids content) of 1 to 50 wt .-%, preferably 3 to 45 wt .-%, particularly preferably 3 to 35 wt .-%, based on the composition on.
  • composition according to the invention by a content of particulate metals and / or metal compounds in the composition 1 to 95 wt .-%, preferably 3 to 90 wt .-%, particularly preferably 5 to 85 wt .-%, most preferably 10 bis 80 wt .-%, characterized.
  • the particulate additives advantageously have a particle size of 5 nm to 50 .mu.m, preferably from 10 nm to 40 .mu.m, more preferably from 15 nm to 30 .mu.m.
  • the determination of the particle size can, for. For example, using CAMSIZER, HORIBA LA-30, LB-550 and LA-950 from Retsch Technology. Thus, the particle size can be determined wet from 1 nm and dry from 100 nm.
  • the conductive additives protect against corrosion when used in sufficient concentration and in contact with the metal substrate.
  • metal substrates which are protected against corrosion by a coating of particulate metals can advantageously be welded.
  • compositions of the invention may additionally contain additives, advantageously selected from the series of defoamers, thickeners, rheology aids, dispersion aids, anti-settling agents, rust inhibitors, wetting agents, organic pigments, polymers or polymer dispersions and the catalysts for the condensation and curing.
  • additives advantageously selected from the series of defoamers, thickeners, rheology aids, dispersion aids, anti-settling agents, rust inhibitors, wetting agents, organic pigments, polymers or polymer dispersions and the catalysts for the condensation and curing.
  • additives advantageously selected from the series of defoamers, thickeners, rheology aids, dispersion aids, anti-settling agents, rust inhibitors, wetting agents, organic pigments, polymers or polymer dispersions and the catalysts for the condensation and curing.
  • polymers for example, but not exclusively, acrylate dispersions, PU dispersions, epoxy resin dispersions, functionalized polyesters
  • organic film formers and adhesion promoters based on acrylic acid esters acrylic polyester-polyurethane copolymers, ethylene-acrylic copolymers, polyester resins can be used with free carboxyl groups.
  • compositions according to the invention can be obtained by a content of additives of in each case 0 to 5% by weight, in particular of thickeners of 0 to 5% by weight and / or of antisettling agents of 0 to 5% by weight and / or wetting agents of 0 up to 3% by weight and / or of corrosion inhibitor from 0 to 1% by weight, based in each case on the composition, the sum of all components in the composition giving 100% by weight.
  • Typical thickeners are z.
  • polyacrylic acid polymers cellulose ethers, polyurethanes, acrylate polymers, hydroxyethyl cellulose, in concentrations of 0.005 to 4.0 wt .-%, preferably from 0.008 to 3.0 wt .-% and most preferably from 0.01 to 2.0 wt .-% are used.
  • thickeners or rheology modifiers are u. a. Coapur 6050 and Coapur XS 71 from Coatex.
  • anti-settling agents are u. a. Laponite, bentonites, glycerol stearates, polyamides, xanthan gum, polyethylene waxes, modified and unmodified fumed silica, for example Aerosil® R 812 S or Aerosil® R 805, which are also present in concentrations of up to 4% by weight, preferably 0.01 to 3% by weight. %, in particular from 0.1 to 2 wt .-% are used.
  • wetting agents are z.
  • Typical corrosion inhibitors are molybdate, phosphates, chromates, borates and in particular organic corrosion inhibitors.
  • the organic corrosion inhibitors are used in lower concentrations, suitably up to 1.0 wt .-%, preferably 0.8 wt .-%, particularly preferably 0.5 wt .-%, in particular from 0.00001 to 0.1 wt. -%, in each case based on the composition, wherein the sum of all components in the composition give 100 wt .-%.
  • Possible catalysts for the condensation and curing are z. TYZOR LA (DuPont), titanium acetylacetonate, tetrakis (triethanolamine) zirconate.
  • the present invention further provides a process for the preparation of a composition according to the invention, which comprises firstly a binder comprising at least one co-condensate based on an ⁇ -glycidyloxyalkylalkoxysilane of the formula I X-Si (R 2 ) x (OR 1 ) 3-x (I), wherein X is a 2- (3,4-epoxycyclohexyl) ethyl, 1-glycidyloxymethyl, 2-glycidyloxyethyl, 3-glycidyloxypropyl or 3-glycidyloxyisobutyl group, R 1 and R 2 are each independently linear or branched Alkyl group having 1 to 4 carbon atoms, and x is 0 or 1, and at least one bis (alkoxysilylalkyl) amine of the general formula II (OR 1 ) 3 Si - A - Si (OR 1 ) 3 (II), wherein the groups R 1 are identical or different and R 1
  • the ⁇ -glycidyloxyalkylalkoxysilane of the formula I in a molar ratio to the bis (alkoxysilylalkyl) amine of the general formula II of from 0.1 to 99.9 to 99: 1, preferably from 1 to 99 to 95 to 5, particularly preferably to 80 to 20, very particularly preferably to 70 to 30, in particular one sets the ⁇ -Glycidyloxyalkylalkoxysilan in the binder with 0.001 to 42 mol%, preferably from 0.01 and 30 mol%, more preferably from 0.1 to 15 mole%, most preferably from 0.2 to 1.5 mole%.
  • water is used in a molar excess, based on the silanes used according to formulas I and II and optionally the abovementioned silicon compounds, suitably 2 to 1000 mol of water, preferably 5 to 500 mol, in particular 10 to 100 moles of water per mole of the present Si-bonded alkoxy groups of the silanes used, under protective gas presents.
  • the protective gas used is usually nitrogen or argon.
  • an organic or inorganic acid can be used in carrying out the process according to the invention, this being advantageously selected from the series formic acid, acetic acid, propionic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid.
  • Said acids can be used in aqueous but also in concentrated form.
  • the pH of the reaction or product mixtures, in particular of the binder, during and / or after the reaction to 1 to 6.5, preferably 2 to 6, in particular to 2 , 5; 3; 3.5; 4; 4.5; 5 and 5.5 set advantageous.
  • binders used according to the invention can also be stabilized in the neutral and alkaline ranges.
  • the pH can be advantageously neutral and alkaline, in particular 7; 7,5, 8; 8.5; 9; 9.5; 10; 10.5; 11; 11.5; 12; 12.5; 13 and 14, adjust, cf. the examples.
  • Other bases in addition to alkali lye such as aqueous NaOH or KOH, which can be advantageously used, are preferably N, N-dimethyl-ethanolamine or TYZOR TEAZ [tetrakis (triethanolamine) zirconate].
  • ⁇ -glycidyloxyalkylalkoxysilane of the formula I is preferably 3-glycidyloxypropyltrimethoxysilane and / or 3-glycidyloxypropyltriethoxysilane and metered into the acidic aqueous mixture obtained above and the mixture is heated for 0.1 to 3 hours, preferably 0.5 to 1.5 or 2 hours, with stirring or mixing to a temperature of 50 to 90 ° C, preferably 55 to 70 ° C, in particular 60 to 65 ° C.
  • the bis (trimethoxysilylpropyl) amine and / or bis (triethoxysilylpropyl) amine are preferably added to the heated, acidic mixture containing .omega.-glycidyloxyalkylalkoxysilane.
  • a tetraalkoxysilane preferably tetramethoxysilane, tetraethoxysilane
  • an alkylalkoxysilane preferably C 1 -C 16 -alkylalkoxysilanes, in particular methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane (PTMO), n-propyltrimethoxysilane Propyltriethoxysilane (PTEO), i-butyltrimethoxysilane (IBTMO), i-butyltriethoxysilane (IBTEO), octyltrimethoxysilane (OCTMO), octyltriethoxysilane (OCTEO), mercaptoalkylalkoxysi
  • the dosing of the abovementioned silanes is advantageously carried out at a pH of 2 to 6, preferably 3 to 5, and with stirring at 50 to 90 ° C, preferably 60 to 65 ° C.
  • the mixture is then allowed to react for a further 0.3 to 6 hours, preferably 2 to 4 hours, while stirring is possible; d. H.
  • the alkoxysilanes used thereby hydrolyze substantially completely hydrolyzed and condensed or co-condensed.
  • the hydrolysis alcohol formed in the reaction can then be removed, at least proportionally, from the reaction mixture with, as a rule, portions of water under reduced pressure (vacuum distillation).
  • the binder thus present may optionally be diluted with water and / or an aqueous acid or aqueous base, for example, the pH, the To set the content of dry residue and / or the viscosity. Subsequently, the binder is suitably filtered, preferably using a fine-pored filter plate to separate coarser in the reaction optionally resulting aggregates.
  • a binder obtainable at room temperature usually has an oily consistency, is slightly cloudy to clear and from yellowish to colorless.
  • At least one additive from the series of particulate metals and / or metal alloys already disclosed above can now be dispersed in the binder thus obtained, and optionally at least one additive, as also set out above, can be stirred in.
  • an organic or inorganic acid according to the invention selected from the series formic acid, acetic acid, propionic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and an aqueous base selected from the series caustic soda, potassium hydroxide or "TYZOR TEAZ" [tetrakis (triethanolamine) zirconate] or N, N-dimethylethanolamine or other bases are preferably used, wherein the pH during and / or after the reaction in the binder and / or after formulation in the composition to 1 to 14, preferably 2 to 12, particularly preferably 2.5 to 9, more preferably 3 to 8, in particular 3.5; 4; 4.5; 5; 5.5; 6; 6.5; 7; 7.5; 8 and 8.5, wherein the addition of at least one of the above-mentioned particulate metals, metal alloys and / or metal compounds to the binder can lead to a change in the pH, in particular the addition of zinc, zinc oxide, zinc alloys, magnesium, aluminum , Magn
  • a composition according to the invention can be prepared in suitable mixers or mixing units known per se to the person skilled in the art.
  • the present invention furthermore relates to the use of a composition according to the invention or obtainable according to the invention for coatings which cure in the air at a temperature of 16 to 26 ° C., particularly advantageous for coatings of metals and metal alloys to protect against corrosion.
  • compositions according to the invention are particularly advantageously characterized by a comparatively excellent processing stability and outstanding user and environmentally friendly properties for corrosion protection applications on metal substances.
  • the pH of the reaction mixtures was determined by means of a pH paper (special indicator pH 2.5-4.5, Merck, pH-Fix 0.0-6.0, Machery-Nagel)
  • the determination of the pH values in the binders and the compositions formulated therefrom were alternatively carried out with a pH meter, Metrohm 826 pH mobile.
  • the formulations were diluted 1: 1 with water before measurement.
  • a milky turbid liquid with a pH of 3.9 was obtained.
  • a milky cloudy liquid with a pH of 4.0 was obtained.
  • a milky turbid liquid with a pH of 4.3 was obtained.
  • a milky turbid liquid with a pH of 4.2 was obtained.
  • a milky turbid liquid with a pH of 4.3 was obtained.
  • a milky turbid liquid with a pH of 4.2 was obtained.
  • a cloudy light beige liquid with a pH of 5.0 was obtained.
  • the weight of the residue was 1347.82 g.
  • the batch was again removed by distillation at about 180 mbar 36.19 g alcohol / water mixture and mixed with 51.22 g of deionized water.
  • the cooled residue was filtered through a Seitz T-950 filter plate.
  • the weight of the residue was 1347.82 g.
  • a milky white liquid with a pH of about 4.3 was obtained.
  • the cooled residue was filtered through a Seitz T-950 filter plate.
  • the weight of the residue was 1308.51 g.
  • a milky white liquid with a pH of about 4.0 was obtained.
  • a clear, yellowish liquid with a pH of 3.9 was obtained.
  • the product is stable for at least 6 months.
  • the pH of samples of the acidic aqueous binders of Examples 2, 3, 6, 7 and 8 were adjusted to pH 12 with a 10% aqueous KOH solution. The addition of alkali was carried out rapidly.
  • the examples marked “stable" in the table were stable for at least one week at the indicated pH.
  • the steel test panels were cleaned with an organic solvent (ethyl acetate) and then placed in an alkaline cleaning bath (composition: 10.0 g / l S 5610 (Chemetall), pH 11.5, 60 ° C, 35 sec). After alkaline cleaning, the metal substrates were rinsed with deionized water. The excess water was blown off the surface with a compressed air gun.
  • organic solvent ethyl acetate
  • alkaline cleaning bath composition: 10.0 g / l S 5610 (Chemetall), pH 11.5, 60 ° C, 35 sec.
  • the corrosion tests (also called NSS for short) were carried out in a salt spray (test according to DIN 50021-SS).
  • the additives B and C were prepared in the universal mixing device (machine type AM 501 T from Hauschild).
  • the additive mixtures B and C were each mixed 3 x 30 sec at 3000 rpm in the universal mixer.
  • compositions for the comparative application examples were carried out in a universal mixing device (machine type AM 501 T from Hauschild)
  • compositions or compositions prepared in accordance with Tables 1 and 2 were applied to the prepared steel test panels by means of a paint dumbbell having a wet layer thickness of 80 ⁇ m, cf. Item 1, applied.
  • the plates were dried at 20 ° C for 24 hours and scribed.
  • the adhesion of the coated substrates was tested by cross-cut test.
  • coated and scribed substrates in salt spray were tested for corrosion resistance and assessed.
  • the sample from Application Example 3 was coated with a 2K epoxy resin: Standox, EP Primer Filler and Standox EP Hardener. Mixing ratio 2: 1 (according to instructions).
  • the coating system was applied using a doctor blade (80 ⁇ m wet film thickness, ⁇ 30 ⁇ m dry film thickness) and cured at 20 ° C. for 24 hours.
  • a comparative sample (only cleaned steel sheet) was also coated.
  • Crosshatch Sample 1 Application Example 3 + epoxy resin coating
  • Crosshatch Sample 2 (steel sheet + epoxy resin coating): 0
  • Both samples were scratched with 1 mm Ritzer and examined in the salt spray for corrosion. After 200 hours, Sample 2 showed massive corrosion at the scribe and spalling, while Sample 1 was also corrosion free at the scribe.
  • Application example 6 shows no corrosion at the scribe after 17 hours, after 150 hours partly corrosion at the scribe and after 250 hours almost continuous corrosion at the scribe.
  • the surface is corrosion-free.
  • Application Example 7 shows no corrosion at the scribe after 19 hours in the salt spray. However, a continuous corrosion can be detected at the scribe after 135 hours.

Claims (14)

  1. Composition contenant
    - un liant contenant au moins un produit de co-condensation à base d'un co-glycidyloxyalkylalcoxysilane de formule I

            X-Si(R2)x(OR1)3-x     (I),

    dans laquelle X représente un groupe 2-(3,4-époxycyclohexyl)éthyle, 1-glycidyloxyméthyle, 2-glycidyloxyéthyle, 3-glycidyloxypropyle ou 3-glycidyloxyisobutyle, R1 ainsi que R2 représentent indépendamment l'un de l'autre un groupe alkyle linéaire ou ramifié ayant de 1 à 4 atomes de carbone, et x est égal à 0 ou 1,
    et au moins une bis(alcoxysilylalkyl)amine de formule générale II

            (OR1)3Si - A - Si(OR1)3     (II),

    dans laquelle les groupes R1 sont identiques ou différents et R1 représente un groupe alkyle linéaire ou ramifié ayant de 1 à 4 atomes de carbone et A représente un groupe à fonction bis-amino de formule

            - (CH2)i-[NH(CH2)f]gNH[(CH2)f*NH]g*-(CH2)i*-     (IIa)

    dans laquelle i, i*, f, f*, g ou g* sont identiques ou différents, avec i et/ou i* = 1, 2, 3 ou 4, f et/ou f* = 1 ou 2, g et/ou g* = 0 ou 1,
    ainsi qu'en option au moins un autre composé de silicium de la série tétraalcoxysilane, alkylalcoxysilane, mercaptoalkylalcoxysilane, carboxyalkylalcoxysilane, aminoalkylalcoxysilane, uréidoalkylalcoxysilane, thiocyanatoalkylalcoxysilane et des sols de silice,
    - de l'eau,
    - un alcool en une quantité de moins de 3 % en poids, par rapport à la composition,
    - au moins un ajout de la série des métaux et/ou alliages métalliques particulaires, l'ajout de la série des métaux et/ou alliages métalliques particulaires étant choisi dans la série constituée par la poudre de zinc, les lamelles de zinc, la poussière de zinc, la poudre ou les lamelles ou la poussière d'alliages de zinc, les alliages bismuth-zinc, et
    - en option au moins un additif,
    le pH de dans la composition valant de 1 à 14 et le résidu sec du liant valant de 1 à 50 % en poids, par rapport au liant utilisé.
  2. Composition selon la revendication 1,
    pour laquelle dans la préparation du liant on dispose au préalable de l'eau en un excès molaire par rapport aux silanes de formules I, II utilisés, ainsi qu'éventuellement aux composés de silicium précités, et on ajuste à un pH acide par addition d'un acide organique ou inorganique et en option on ajoute en outre un sol de silice,
    on ajoute par addition dosée un ω-glycidyloxyalkylalcoxysilane de formule I et on chauffe,
    en option on ajoute ensuite par addition dosée un acide et on ajoute par addition dosée au moins une bis(alcoxysilylalkyl)amine de formule générale II ainsi qu'en option au moins un autre composé de silicium de la série tétraalcoxysilane, alkylalcoxysilane, mercaptoalkylalcoxysilane, carboxyalkylalcoxysilane, aminoalkylalcoxysilane, uréidoalkylalcoxysilane et thiocyanatoalkylalcoxysilane et on fait réagir,
    ensuite on sépare sous pression réduite du mélange réactionnel au moins en partie l'alcool d'hydrolyse ainsi formé,
    en option on dilue avec de l'eau et/ou un acide aqueux le liant ainsi obtenu et ensuite on le filtre,
    le résidu sec du liant valant de 1 à 50 % en poids, de préférence 5 à 40 % en poids, de façon particulièrement préférée 8 à 35 % en poids, en particulier 10 à 25 % en poids, par rapport au liant utilisé.
  3. Composition selon la revendication 1 ou 2,
    caractérisée par
    un résidu sec (teneur en matière solide) de 1 à 50 % en poids, de préférence 3 à 45 % en poids, de façon particulièrement préférée 3 à 35 % en poids, par rapport à la composition.
  4. Composition selon l'une quelconque des revendications 1 à 3,
    caractérisée en ce que
    la teneur de la composition en les métaux et/ou alliages métalliques particulaires vaut de 1 à 95 % en poids, de préférence de 3 à 90 % en poids, de façon particulièrement préférée de 5 à 85 % en poids, de façon tout particulièrement préférée de 10 à 80 % en poids.
  5. Composition selon l'une quelconque des revendications 1 à 4,
    caractérisée en ce que
    les additifs sont choisis dans la série des antimousses, épaississants, adjuvants de rhéologie, adjuvants de dispersion, agents anti-sédimentation, antirouilles, agents mouillants, pigments organiques, polymères ou dispersions de polymères ainsi que des catalyseurs pour la condensation et le durcissement.
  6. Composition selon l'une quelconque des revendications 1 à 5,
    caractérisée par
    une teneur en additifs, en particulier en épaississant de 0 à 5 % en poids et/ou en agent anti-sédimentation de 0 à 5 % en poids et/ou en agent mouillant de 0 à 3 % en poids en agent anticorrosion de 0 à 1 % en poids chacun par rapport à la composition, la somme de tous les composants présents dans la composition étant égale à 100 % en poids.
  7. Procédé pour la préparation d'une composition selon l'une quelconque des revendications 1 à 6,
    caractérisé en ce que
    d'abord on prépare un liant contenant au moins un produit de co-condensation à base d'un ω-glycidyloxyalkylalcoxysilane de formule I

            X-Si(R2)x(OR1)3-x     (I),

    dans laquelle X représente un groupe 2-(3,4-époxy-cyclohexyl)éthyle, 1-glycidyloxyméthyle, 2-glycidyloxyéthyle, 3-glycidyloxypropyle ou 3-glycidyloxyisobutyle, R1 ainsi que R2 représentent indépendamment l'un de l'autre un groupe alkyle linéaire ou ramifié ayant de 1 à 4 atomes de carbone, et x est égal à 0 ou 1,
    et
    au moins une bis(alcoxysilylalkyl)amine de formule générale II

            (OR1)3Si - A - Si(OR1)3     (II),

    dans laquelle les groupes R1 sont identiques ou différents et R1 représente un groupe alkyle linéaire ou ramifié ayant de 1 à 4 atomes de carbone et A représente un groupe à fonction bis-amino de formule

            - (CH2)i-[NH(CH2)f]gNH[(CH2)f*-NH]g*-(CH2)i*-     (IIa)

    dans laquelle i, i*, f, f*, g ou g* sont identiques ou différents, avec i et/ou i* = 1, 2, 3 ou 4, f et/ou f* = 1 ou 2, g et/ou g* = 0 ou 1,
    ainsi qu'en option au moins un autre composé de silicium de la série tétraalcoxysilane, alkylalcoxysilane, mercaptoalkylalcoxysilane, carboxyalkylalcoxysilane, aminoalkylalcoxysilane, uréidoalkylalcoxysilane, thiocyanatoalkylalcoxysilane et des sols de silice,
    en
    disposant au préalable de l'eau en un excès molaire par rapport aux silanes de formules I, II utilisés, ainsi qu'éventuellement aux composés de silicium précités, et en ajustant à un pH acide par addition d'un acide organique ou inorganique et en option en ajoutant en outre sous agitation un sol de silice,
    en ajoutant par addition dosée un ω-glycidyloxyalkylalcoxysilane de formule I et en chauffant,
    en option en ajoutant ensuite par addition dosée un acide
    et en ajoutant par addition dosée au moins une bis(alcoxysilylalkyl)amine de formule générale II ainsi qu'en option au moins un autre composé de silicium de la série tétraalcoxysilane, alkylalcoxysilane, mercaptoalkylalcoxysilane, carboxyalkylalcoxysilane, aminoalkylalcoxysilane, uréidoalkylalcoxysilane et isocyanatoalkylalcoxysilane et en faisant réagir, ensuite en séparant sous pression réduite du mélange réactionnel au moins en partie l'alcool d'hydrolyse ainsi formé,
    en option en diluant ou respectivement ajustant le pH avec de l'eau et/ou avec un acide aqueux et/ou une base aqueuse le liant ainsi obtenu et ensuite en le filtrant,
    et
    en dispersant dans le liant ainsi obtenu au moins un ajout de la série des métaux et/ou alliages métalliques particulaires et en option en délayant au moins un additif et en option en ajustant le pH dans la composition.
  8. Procédé selon la revendication 7,
    caractérisé en ce
    qu'on utilise l'ω-glycidyloxyalkylalcoxysilane de formule I en un excès molaire par rapport à la bis(alcoxysilylalkyl)amine de formule générale II de 0,1 : 99,9 à 99 : 1, en particulier on utilise l'ω-glycidyloxyalkylalcoxysilane dans le liant à une concentration de 0,001 à 42 % en moles, de préférence de 0,01 à 30 % en moles, de façon particulièrement préférée de 0,1 à 15 % en moles, de façon tout particulièrement préférée de 0,2 à 1,5 % en moles.
  9. Procédé selon la revendication 7 ou 8,
    caractérisé en ce
    qu'on dispose au préalable sous un gaz protecteur l'eau en un excès molaire, par rapport aux silanes de formules I et II utilisés ainsi qu'en option aux composés de silicium précités, convenablement de 2 à 1 000 moles d'eau, de préférence de 5 à 500 moles d'eau, en particulier de 10 à 100 moles d'eau par mole des groupes alcoxy présents, liés à Si, des silanes utilisés, la réaction étant effectuée de préférence sous azote ou argon.
  10. Procédé selon l'une quelconque des revendications 7 à 9,
    caractérisé en ce que
    l'acide organique ou inorganique est choisi dans la série constituée par l'acide formique, l'acide acétique, l'acide propionique, l'acide chlorhydrique, l'acide nitrique, l'acide sulfurique, l'acide phosphorique, et la base aqueuse est choisie dans la série constituée par une solution d'hydroxyde de sodium, une solution d'hydroxyde de potassium, la N,N-diméthyléthanolamine, le zirconate de tétrakis-(triéthanolamine), et on ajuste le pH pendant et/ou après la réaction dans le liant et/ou après formulation dans la composition à 1 à 14, de préférence 2 à 12, de façon particulièrement préférée 2,5 à 9, de façon tout particulièrement préférée 3 à 8, en particulier à 3,5 ; 4 ; 4, 5 ; 5 ; 5, 5 ; 6 ; 6, 5 ; 7 ; 7, 5 ; 8 ainsi que 8,5, l'addition du métal ou de l'alliage métallique particulaire au liant pouvant conduire à une modification du pH, de préférence, dans le cas d'addition de zinc ou d'un alliage de zinc, à un liant ajusté à un pH acide.
  11. Procédé selon l'une quelconque des revendications 7 à 10,
    caractérisé en ce
    qu'en tant qu'ω-glycidyloxyalkylalcoxysilane de formule I on introduit comme charge ou ajoute par addition dosée du 3-glycidyloxypropyltriméthoxysilane et/ou du 3-glycidyloxypropyltriéthoxysilane et on chauffe pendant 0,1 à 3 heures, de préférence 0,5 à 2 heures le mélange aqueux acide obtenu, sous agitation ou mélangeage, à une température de 50 à 90 °C, de préférence de 60 à 65 °C.
  12. Procédé selon l'une quelconque des revendications 7 à 11,
    caractérisé en ce
    qu'on ajoute par addition dosée au mélange chauffé, acide et contenant un ω-glycidyloxyalkylalcoxysilane, à un pH de 2 à 6, de préférence de 3 à 5, de la bis(triméthoxysilylpropyl)amine et/ou de la bis(triéthoxysilylpropyl)amine et en option en tant qu'autre composé de silicium un tétraalcoxysilane, de préférence du tétraméthoxysilane, du tétraéthoxysilane, un alkylalcoxysilane, de préférence un alkyl(C1-C16)-alcoxysilane, en particulier du méthyltriméthoxysilane, du méthyltriéthoxysilane, du n-propyltriméthoxysilane (PTMO), du n-propyltriéthoxysilane (PTEO), de l'isobutyltriméthoxysilane (IBTMO), de l'isobutyl-triéthoxysilane (IBTEO), de l'octyltriméthoxysilane (OCTMO), de l'octyltriéthoxysilane (OCTEO), un mercaptoalkylalcoxysilane, de préférence du 3-mercapto-propyltriméthoxysilane (MTMO), du mercaptopropyl-triméthoxysilane (MTEO), un amidoalkylalcoxysilane, de préférence du 3-aminopropyltriméthoxysilane (AMMO), du 3-aminopropyltriéthoxysilane (AMEO), du N-(2-amino-éthyl)-3-aminopropyltriméthoxysilane (DAMO), du N-(2-aminoéthyl)-3-aminopropyltriéthoxysilane, du N,N'-diaminoéthyl-3-aminopropyltriméthoxysilane (TriAMO), du N,N'-diaminoéthyl-3-aminopropyltriéthoxysilane, un carboxyalkyltrialcoxysilane, un uréidoalkylalcoxysilane, de préférence du 3-uréidopropyltriméthoxy-silane, du 3-uréidopropyltriéthoxysilane et/ou un thiocyanatoalkylalcoxysilane, de préférence du 3-thiocyanatopropyltriméthoxysilane, du 3-thiocyanatopropyltriméthoxysilane, et on fait réagir pendant 0,3 à 6 heures, de préférence 1 à 4 heures, sous agitation, à une température de 50 à 90 °C, de préférence de 60 à 65 °C, c'est-à-dire que les alcoxysilanes utilisés sont pratiquement totalement hydrolysés et condensés ou co-condensés.
  13. Utilisation d'une composition selon l'une quelconque des revendications 1 à 6 ou préparée selon l'une quelconque des revendications 7 à 12, pour des revêtements qui durcissent à l'air à une température de 16 à 26 °C.
  14. Utilisation selon la revendication 13 pour des revêtements de métaux et d'alliages métalliques pour la protection contre la corrosion.
EP12706821.1A 2011-03-25 2012-02-27 Formulation aqueuse anticorrosion à base de silane Active EP2689051B1 (fr)

Priority Applications (1)

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DE102011006182 2011-03-25
DE201110084183 DE102011084183A1 (de) 2011-03-25 2011-10-07 Wässrige Korrosionsschutzformulierung auf Silanebasis
PCT/EP2012/053256 WO2012130544A1 (fr) 2011-03-25 2012-02-27 Formulation aqueuse anticorrosion à base de silane

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EP2689051B1 true EP2689051B1 (fr) 2018-01-17

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JP2015232143A (ja) 2015-12-24
DE102011084183A1 (de) 2012-09-27
US20190153238A1 (en) 2019-05-23
SG10201602119QA (en) 2016-04-28
SG193573A1 (en) 2013-11-29
DK2689051T3 (en) 2018-04-23
WO2012130544A1 (fr) 2012-10-04
PL2689051T3 (pl) 2018-07-31
KR20130133058A (ko) 2013-12-05
JP5936674B2 (ja) 2016-06-22
US11168221B2 (en) 2021-11-09
ES2661233T3 (es) 2018-03-28
KR101678267B1 (ko) 2016-12-06
US20140106176A1 (en) 2014-04-17
JP2014515771A (ja) 2014-07-03
EP2689051A1 (fr) 2014-01-29

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